CHEM 221, Lecture 1-1 First Law of Thermodynamics: Basic Concepts

1
The First Law of Thermodynamics, Chapter 2

General Objective
Overview of basic concepts of thermodynamics learnt in first-year chemistry;
Conservation of energy and energy changes that accompany physical and chemical
processes; Change of energy through work or heat; Enthalpy is the main theme
Thermodynamics study of the transformation of energy.

System and Surroundings

System: part of the universe that is explored (studied)
Surroundings: region outside the system separated by a boundary

Types of systems


CHEM 221, Lecture 1-1 First Law of Thermodynamics: Basic Concepts

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Work, Heat, and Energy

Work is done when an object moves against an opposing force (e.g. gas expansion,
electric motor)

Energy of a system is its capacity to do work

Heat is the energy transferred between the system (T
1
) and its surroundings (T
2
) as a
result of temperature difference

Boundaries
(a) diathermic a change of state is observed when two objects (T
1
and T
2
) are in
contact; (b) adiabatic no change occurs

Exothermic process: a process that releases energy as heat (e.g. combustion reaction)

Endothermic process: a process that absorbs energy as heat (e.g. vaporization of
water)

CHEM 221, Lecture 1-1 First Law of Thermodynamics: Basic Concepts

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Molecular Interpretation of Heat and Work

Heating: transfer of energy that makes use of disorderly molecular motion in the
surroundings

Thermal motion is the disorderly motion of molecules

Figure: energy transferred as heat from the system into the
surroundings stimulates the thermal (disordered) motion of
molecules




Figure: energy transferred as work from the system into the
surroundings stimulates organized motion of molecules

Observation: following the work done, collisions between molecules
quickly randomize the directions in which the molecules in the
surroundings move

CHEM 221, Lecture 1-1 First Law of Thermodynamics: Basic Concepts

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The First Law

Internal energy (U) the total energy (kinetic energy + potential energy) of all the
molecules in the system

Internal energy change: AU = U
f
U
i


U is a state function its value depends on the current state and is independent of
how the state has been prepared

Unit of work, heat, internal energy the joule [J]; 1 J = 1kg m
2
s
2


Other units: 1 eV = 1.602 10
-19
C 1V = 0.1602 aJ per atom or molecule

N
A
(6.022 10
23
mol
-1
) = 96.5 10
4
J mol
-1
~ 100 kJ mol
-1


1 eV per atom/molecule ~ 100 kJ mol
-1
of atoms/molecules

1 cal = 4.184 J

Molar internal energy: U
m
= U/n Unit of U
m
: J mol
1


CHEM 221, Lecture 1-1 First Law of Thermodynamics: Basic Concepts

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Molecular Interpretation of Internal Energy

Molecules translate (the motion of its centre of mass through space), rotate (around
its centre of mass), or vibrate (bond lengths and angles change but the centre of mass
remains is unmoved)

The average energy of each quadratic contribution to the energy is (equipartition
theorem) kT

Mean energy of the atoms free to move in three dimensions: 3/2 kT per atom

One mole of atoms

3/2 kT N
A
= 3/2 RT

RT 2 / 3 ) 0 ( U (T) U
m m
+ = (monoatomic gas; translation)

U
m
(0) is the molar internal energy at T = 0 K

One mole of molecules: the effect of rotation and vibration need to be considered

CHEM 221, Lecture 1-1 First Law of Thermodynamics: Basic Concepts

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Linear molecule (e.g. N
2
and CO
2
) can rotate around two axes
perpendicular to the line of the atoms (see Figure)

Nonlinear molecule (e.g. CH
4
and H
2
O) can rotate around three axes
perpendicular to the line of the atoms (see Figure)



Each rotational mode contributes kT to U

RT 2 / 5 ) 0 ( U (T) U
m m
+ = (linear molecule; translation and rotation)

RT 3 ) 0 ( U (T) U
m m
+ = (nonlinear molecule; translation and rotation)

Molecules do not vibrate significantly at room temperature the contribution of
molecular vibrations to U is negligible (exception: very large molecules, e.g.
polymers and biological macromolecules)

Important: there are no intermolecular interactions (perfect gas); the distance between
the molecules has no effect on U; U a perfect gas is independent of V it occupies

CHEM 221, Lecture 1-1 First Law of Thermodynamics: Basic Concepts

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Conservation of energy

Internal energy changed by: (i) doing work (w) on the system
(ii) heating the system (q)
System feels energy input, not its mode



First Law of Thermodynamics:
The internal energy (U) of an isolated system is constant

w q 8 + =

Internal energy change by: (i) heat transfer through the boundary
(ii) work
w > 0, q > 0 energy transferred to the system
w < 0, q < 0 energy lost from the system

CHEM 221, Lecture 1-1 First Law of Thermodynamics: Basic Concepts

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Work and Heat

Infinitesimal internal energy change, dU:

dw dq dU + =

dq heat supplied to the system; dw work done on the system

Expansion work

Origin of expansion work change in volume due to gas expansion (V increase)

Examples

1. Thermal decomposition of CaCO
3
:
2
heating
3
CO CaO CaCO +
2. Hydrocarbon combustion: O H 5 CO 4 O 2 / 13 H C
2 2 2 10 4
+ +


CHEM 221, Lecture 1-1 First Law of Thermodynamics: Basic Concepts

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Work general expression


Object of mass m moves a distance (dz) against an opposing force (F); negative sign
internal energy (U) decreases as the system does work (w)

dz F dw =


External force acting on the piston: F = p
ex
A

Work done by the system: dw = p
ex
A dz = p
ex
dV


}
=
f
i
V
V
ex
dV p w


F
dz
CHEM 221, Lecture 1-1 First Law of Thermodynamics: Basic Concepts

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Other types of work

Intensive factor extensive factor



Free expansion

- expansion against p
ex
= 0 w = 0

- no work is done when system expends freely expansion into a vacuum
CHEM 221, Lecture 1-1 First Law of Thermodynamics: Basic Concepts

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Expansion against constant pressure

p
ex
= const (expansion against atmospheric pressure)

( )
i f ex
V
V
ex
V V p dV p w
f
i
= =
}

9 p w
ex
=

indicator diagram p,V-graph to illustrate work

work area under the p
ex
line



Example

expansion of gas generated in a chemical reaction




CHEM 221, Lecture 1-1 First Law of Thermodynamics: Basic Concepts

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(d) Isothermal Reversible expansion

Reversible change a change that can be reversed by
an infinitesimal modification of a variable

Equilibrium a system is in equilibrium with surroundings if an infinitesimal change
in the conditions in opposite directions results in opposite changes

Example

Thermal equilibrium of two objects

Gas confined by a piston; system in mechanical equilibrium with its surroundings

at each stage of expansion: p
ex
= p

dV p dV p dw
ex
= =


}
=
f
i
V
V
dV p w p = f(V)
Perfect gas: pV = nRT equation of state
CHEM 221, Lecture 1-1 First Law of Thermodynamics: Basic Concepts

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(e) Isothermal reversible expansion

Isothermal (T = const), perfect gas p = nRT / V

V volume at a given stage of expansion

} }
= =
f
i
f
i
V
V
V
V
V
dV
nRT dV p w
i
f
V
V
ln nRT w =

- V
f
> V
i
w < 0 (system does the work and its internal
energy decreases)

indicator diagram p,V-graph to illustrate work

- work area under the isotherm nRT/V p =

- more work is done by a reversible expansion

- reversible expansion maximum work that can be done
CHEM 221, Lecture 1-1 First Law of Thermodynamics: Basic Concepts

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Blackboard Example (Atkins, de Paula): Calculate the work done when 50.0 g of Fe
reacts with HCl to produce H
2
in (a) a closed vessel (V = const), (b) an open beaker
(p
ex
= const) at 25 C.

(g) H (aq) FeCl HCl(aq) 2 Fe(s)
2 2
+ +







Blackboard Example (Atkins, de Paula): Calculate the expansion work done when
50.0 g of water is electrolyzed under constant pressure and in an open beaker at T =
298 K.